Antistatic finishing of plastic molding materials

ABSTRACT

The use for the antistatic finishing of spun or moulded synthetic polymers of substituted or quaternised compounds derived essentially from high molecular fatty acids and polyalkylene polyamines.

Hochreuter 1 1 Jan. 7, 1975 [5 ANTISTATIC FINISHING 0F PLASTIC [58] Field of Search 260/78 8, 92.8 A, 93.5 A, MOLDING MATERIALS 260/9 3.7, 94.9 GD [75] Inventqr: lslalciltig'galggchreuter, Basel, [56] References Cited UNITEDSTATES PATENTS [73] Asslgnee' f if i i 2,953,420 9/1960 Hees et a]. 8/4 Vase 1 3,122,504 2/1964 Wedell 252/315 22 Filed; s 1 1971 3,230,190 1/1966 Moulton et al..... 260/23 H 3,324,091 6/1967 Savides 260/78 S [21] Appl.No.: 177,161 3,403,117 9/1968 Floyd 260/23 H 'f l Apphcatlon Data. Primary ExaminerHarold Anderson [63] g g y 'g of June Attorney, Agent, or FirmGerald D. Sharkin; Richard E. Vila; Thomas 0. Doyle [30] J l 'IZOIICQIES Apglicatioln :rmnty Data 10181 70 [57] ABSTRACT u y W an "i The use for the antistatic finishing of spun 0r moulded [52] U 5 Cl 260/78 S 26O/92 8 A 260/78 A synthetic polymers of substituted or quaternised com- 26O/93"5 A 266/93 1 260/949 pounds derived essentially from high molecular fatty 260/404'5 acids and polyalkylene polyamines.

. 10 Claims, No Drawings ANTISTATIC FINISHING OF PLASTIC MOLDING R and R denoting a lower carboxylalkyl radical of for- MATERIALS mula This application is a continuation-in-part of applica- [wHThCOOhJMe v tion Ser. No. 158,517, filed June 30, 1971, now aban- 5 where s is l or 2 and Me is a monovalent or multivalent cloned. metal ion, e.g. zinc, magnesium, calcium, and the alkali As is generally known, many plastics including polymetals, have notably good properties for the-antistatic olefins, polystyrene, polyamides and 'polyvinyl chlofinishing of p y efi poly y e e, p lyamides and ride, after conversion into fibre, film or moulded prodp y i y d ucts, accumulate static electricity from external forces For the antistatic finishing of PQ Y and p y which creates difficulty in handling and processing. "Y chloride those compounds of formula in Which- A number of methods have been suggested to prestands f y radical of a fatty acid,

vent or at least minimize this effect. It is known, for exwhich Contains eight to 22 atoms and R 1 and ample, that the application of agents with antistatic R3 each stands for methyl or for M and should not adversely affect the properties of the subproperties to the f c f fib prevents it f Me for'an alkali metal,e.g., sodium, potassium, o'r-lithcoming charged with static electricity, but the protech much torcommenfi them' tion lasts only until the applied film of the agentis yo a speclally for Polyethylene a abraded or dissolved during the service life of the prod- Polypropylene thDSeCOmPOundS, formula (I) t uct. Durable protection can only be achieved by incor- 11-00" stands for the acyl radical of a f l 2 which contains eight to 22 carbon atoms and R R and poration in the polymer agents with effectlve antistatic 2 action which migrate slowly-to the surface ofthe fibre R3 a f stfmds for hydrogen for 2 4Q?v-' or moulded product and inhibit the accumulation of whetrem'p 1 can be employed speclal i static electricity over a long period of time. For practivan cal usefulnesssuch an agent shouldexercise adequate 25 l gzg gg ggfi ggfizgg g 3 33f: 1 21;122: 552; '3} antistatic action when present in small amounts and whichcomprisers thereaction g at C of strate. In particular it has to show good heatstability 1 mole of a polyalkylen'polyamine m and not accelerate the rate of decomposition of the Y i polymer at elevated temperatures. (CHZ)"+NH (CHZ)"'JENH2 It has now-been found that compounds of the formula wherein m andn as defined above,

f n with approximately 1 mole, e.g., 09'l .2 mols, ofa fatty R-co-;Nr1 cm).. -(cH,),.: -N\ acid of formula ReCOOl-I, if necessary withalkylation R3 7 (I) 35 using an alkylating agent-of low molecularweig'ht. I The carboxylic acids of fOrmulaR-CQOH may be where R-CO- stands for the acyl radical of a satusaturated or' unsaturated natural or synthetic fatty rated or unsaturated high molecular weight fatty acid acids, which may be branched but'preferably have a preferably one containing atleast six carbon atoms, R s a g t'cha an hic 'cnn n'a east e.g- Seven R and R each independently of the others stands for 40 to m preferably eight to 22,carbon atoms. The folhydrogen or a low molecularweight, unsubstitutedor o g may be na e e mp cap c, p o ausubstituted alkyl radical, m for 1 to 3 and n for 3 to 5, tie, myristic, palmitic, stearic, cocinic, linoleic, oleic and compounds of theformula and behenic acid. I

pounds in the polymer in amounts of O.01 -5 or preferawherein RCO andmar'e as defined above,

R R R andR are lower alkyl,

A is an anion equivalent, and

qisOor 1 tom, meet the aforesaid requirements and are highly suitable for the antistatic finishing of products spun or moulded from synthetic polymers.

The present invention thus relates to the use of the compoundsof formula (I) for the antistatic finishingof synthetic polymers processed as fibre or mouldedproduct's, which comprises incorporating the said com- R-CO-NH (CH2)n-{-NH(CH ),r] ,,-Nl-I ltis preferable to employ polyalkylene polyamines of formula(ll) in which n is 3 or 4and mis l or 2, examples of which are dipropylene triamine, trip'ropylene tetramine and the corresponding butylene amines, the

first-named being of major interest.

Compounds of formula (I) where each of R R and' R represents-hydrogen or alower carboxyalkyl radical" pound of fonnula bly Oil-l weightpercent on the weightof the polymer. 1

Compounds of formulatl) where RCO- stands for h i m i 1 to 3 d i 3 5 but at least one standsfor a lower carboxyalkylradical, r can'b'e produced by the alkylation of 1 mole of acom- (III) the acyl radical of a fatty acid containing eight to-l8 withl to maximum (m+2) moles of lower halogenalk- Carbon atoms, and R1, z s each for y g n ylc'arboxylic acid such as chloracetic, bromacetic or a lower carboxylalkyl'radical, with at least one of R1, B-chloropropionic acid, or a lower unsaturated, e.g.,

( B-unsaturated, carboxylic acid such as acrylic, methacrylic or crotonic acid. it is advisable to prepare these compounds in the form of the sodium orpotassium salts as these show better storage stability and give very good results in application.

Compounds of formula (I) in which R R and/or R stand for (C,H ,,O),, H wherein x is 2 to 4 and p is l to 5, are formed by alkylation of compounds of formula (Ill), e.g., with alkylene oxides of formula C H O such as ethylene oxide, l ,2-propylene oxide or l,2-butylene oxide.

For the formation of compounds of formula (I) in which R,, R and/or R represent lower unsubstituted alkyl such as methyl or ethyl, compounds of formula (III) are reacted with known alkylating agents such as the alkyl esters. of strong inorganic acids, for instance dialkyl sulphates (dimethyl or diethyl sulphate) or alkyl halides (methyl chloride). If in preparing compound (I) the alkylating agent is employed in excess peralkylation may take place giving compounds which have the formula u. J.L J....'.. v

effective for the claimed use are not invariably ob tained as chemical entities but often as mixtures.

The plastics which are primarily suitable for antistatic finishingaccording to this invention are the thermoplasts, which include the polyamides, polystyrene, polyvinyl chloride. and polyolefins such as are obtained by the highand low-pressure polymerization of ethylene,

propylene, butene-(l) or pentene-(l Several methods are available for incorporating compounds of formula, (I) in plastics. They can be dissolved, suspended or emulsified in a solvent such as ethanol, trichloroethylene, toluene or benzene and mixed with the polymer powder with vigorous stirring, the solvent being subsequently eliminated by distillationor some other suitable means.Alternatively, the compound can be added to the heated polymer melt with thorough mechanical stirring and if necessary the application of pressure, or it can be incorporated in the polymer on a roller mill or in an extruder, as for injec-' tion moulded goods.

It is of advantage to mix the amount of the'com pound of formula I) calculated for a batch of moulding material in a small amount of the polymer and to use thisconcentrated mixture for finishing the batch. Similarly it is of advantage to prepare such concentrated mixtures for storage to be used as required. They can be incorporated inthe batch with or without the addition of solvent.

Antistatic finishing as described in this invention is applicable with every type of product made from synthetic polymers, whether mouldings, film, sheet, filaspinning or moulding machinery.

ment or fibre. If desired the disclosed antistatic com-- pounds can be added in the preforming of plastics materials, which can then be stored in the antistatically finished state, with the advantage that they 'do not be come charged or appreciably charged with static electricity in further handling and processing, e.g., loading into containers, transportation, and passage through Following incorporation of the antistatic compound the materials can be processed by standard methods such as injection or extrusion mouldings, spinning or calendering. v I n addition they may contain other commonly used additives such as plasticizers, dyes, pigments, lubricants or fillers. j

The compounds of formula (I) have good antistatic action and are very stable to heat. The antistatic protection' imparted to the finished products remains effective over a long period of time. They retain their original colour and transparency-and show no tendency to exudation or stickiness.

The antistatic behavior of mouldings finished according to this invention was tested by measuring thesurface resistance at relative humidityand 22 C as specified in German lndustrialStandard 53482.

. In-the following Examples the parts and percentages are by weightand the temperatures in degrees centig'rade,

EXAMPLE 1' 400 Parts of Lupolene 2430-H (registeredtrade mark), a' low density polyethylene with melt index I 1.2-1.7, are mixed with 0.4 parts of a product formed by the condensation reaction of 96.3 parts of capric acid and 65.5 parts of dipropylene jtriamine at 170.

After 20 minutesa homogeneous mixture is obtained which is injection moulded as panels of 1 mm thick ness. The panels are stored for'48 hours at 22 and 65% relativehumidity, after which the surface resistance is measured. The value is"10 Ohms. In the absence of the stated-additive the surface resistance of this grade of polyethylene is 10 Ohms. After ageing-for 16 days at 100 the polyethylene containing the disclosed antistatic agent shows no discoloration, in contrast to an otherwise, identical panel without the incorporated agent;

This-procedure-can be employed with 400 parts of polypropylene (Carlona PM-6l, registered trade mark, melt index 5.0) in place of polyethylene and 2 parts of the aforestated condensation product, the conditions being otherwise the same. The moulded panel finishing with the antistatic compound has a surface resistance of 10 Ohms as compared with 10 Ohms for one without the additive.

EXAMPLE 2 In place of the condensation product used'in the preceding Example, an amide obtained by reaction of 100 parts of lauric acid with 58 parts of dipropylene triamine at ISO- can be incorporated .in Lupolene l8l0l-l in an amount of 0.1% on the weight of the batch. Measured under the same conditions as in Example the surface resistance of a moulding made of this antistatically treated material is 10'. Ohms.

"""tteqs. msiklsrshsmsssm qfly mixed w 2- P r of a product which is formed by the condensation of 100 parts of lauric acid and 58.5 parts of dipropylene triamine at l50-210 and subsequent alkylation with 58 parts of the sodium salt of monochloroacetic acid at 80 in the presence of sodium hydroxide, the product being obtained in the form of the sodium salt. The mixture is injection moulded as panels of 1 mm thickness. The surface resistance is measured as in Example 1, the values being Ohms and 10 Ohms, respectively for the panels with and without the incorporated antistatic agent.

EXAMPLE 4 r 400 Parts of polyvinyl chloride (Basis Solvic 229, registered trade mark) are homogeneously mixed on a laboratory roller mill with 2 parts of a product which is produced by condensation of l l2parts of lauric acid and 58.5 parts of dipropylene triamine at 150-210 and subsequent alkylation with 116.5 parts of the sodium salt of chloroacetic acid at 78-80 in the presence of sodium hydroxide, andis obtained in the form of the sodium salt. The mixture is injection moulded as panels of 1 mm thickness, which are measured for surface resistance as given in Example 1. The value is 10 Ohms for the antistatically finished panel as compared with 10. for one without the stated additive.

Comparable resultsare obtained when a product produced-with 174 parts of chloroacetic acid (sodium salt) in place of,l16.5 finished parts of chloroacetic acid (sodium salt) is used as antistatic agent.

The incorporated antistatic agent does not cause a change of colour in the polyvinyl chloride. After storage for 6 months the antistatically fininshed panels show no tendency to exudation or stickiness.

The 400 parts of polyvinyl chloride can be replaced by"400 parts of polystyrene (HF 77, Monsanto), this being mixedon the roller mill with 6 parts of the product obtained as given in the first paragraphof this Example, The surface resistance of 1 mm thick panels injection moulded with this material is 10 Ohms as compared with 10 Ohms for a panel of the same polystyrene grade containing no antistatic agent.

EXAMPLE 5 On a roller mill 500 parts of polyvinyl chloride (Lonza EN, registered trade mark) are homogeneously blended with 2.5 parts of a product which is formed by condensation of 172.5 parts of capric acid and 1 17 parts of dipropylene triamine at 150-210 followed by methylation with 189 parts of dimethyl sulphate at 80. The mixture is injection moulded as 1 mm thick panels. The surface resistance is measured as in Example 1; it is 10 Ohms as compared with 10 Ohms for a panel without the incorporated antistatic agent.

EXAMPLE 6 400 Partsof polyvinyl chloride (Basis Solvic 229,

Products with particularly good heat stability are obtained when in place of the potassium salt the corresponding magnesium or zinc salt is employed, which can be produced, for-example, bv the addition of an 5 aqueous solution of 28.5 parts of magnesium chloride or 40.8 parts of zinc chloride to 538 parts-of the aforementioned aqueous solution of the potassium salt.

EXAMPLE 7 10 On a roller mill 300 parts of polyvinyl chloride (Lonza SN 60," registered trade mark) are homogeneously mixed with 1.5 parts of a product which is formed by condensation'of l4l parts of oleic acid with 5 7 parts of dipropylene triamine and subsequent alkylation with 58 parts of monochloroacetic acid (sodium salt) in the presence of sodium hydroxide solution and is obtained as the sodium salt. Panels 1 mm thick are injection moulded with the mixture. The surface resistance measured as in Example 1 is 10 Ohms as com- 20 pared with IO Ohms for a panel containing no antistatic agent.

In place of 58 parts of monochloroacetic acid (so-' dium salt), 65 parts of monochloropropionic acid (sodium salt) can be used for alky lating the aforementioned condensation product; the resulting compound having comparable properties.

EXAMPLE 8 dium salt) in the presence of sodium hydroxide solution, the product being in the form of the sodium salt. The mixture is injection moulded as panels of l mm thickness. The surface resistance of these is 10Ohms and 10"Ohms without the incorporated antistatic agent.

having thus disclosed the invention, what we claim is: l. A composition consisting essentially of a synthetic plastic polymer which is selected from'the group consisting of polyamides, polystyrene, polyvinyl chloride, and polyolefins and which has a tendency to accumulate static electricity and, incorporated therein, 0.01 to 5% by weight of the polymer of an antistatic compound of the formula s is l or 2, Me is a monovalent or multivalent metal ion, m is l to '3,

and

n is 3 to 5.

2. A composition according to claim 1 wherein the antistatic compoundispresent in an amount of 0.1 to 1% by weight of the polymer.

3. A composition according to claim 1 wherein the antistatic compound is a compound of the formula and the polymer is a polyamide.

4. A composition according to claim 1 wherein the antistatic compound is a compound of the formula CHzCO ONa CHHMC ONH(CH2)aNH(CHQ)aN and the polymer is polyvinyl chloride.

5. A composition accordingto claim 1 wherein the antistatic compound is a compound of the formula and the polymer polyvinyl chloride. 7

6. A composition according to claim 1 wherein the antistatic compound is a compound of the formula CHzCOOMg 00021! M cimooozn 0111x130 oNmonm-N- olmm omc 0 0 Zn and the polymer is polyvinyl chloride.

8. A composition according to claim 1 wherein the antistatic compound is a compound of the formula and the polymer is polyvinyl chloride.

9. A composition according to claim 1 wherein the antistatic compound is a compound of the formula and the polymer is polyvinyl chloride.

10. A composition according to claim 1 wherein the antistatic compound is a compound of the formula and the polymer is polyvinyl chloride. 

1. A COMPOSITION CONSISTING ESSENTIALLY OF A SYNTHETIC PLASTIC POLYMER WHICH IS SELECTED FROM THE GROUP CONSISTING OF POLYAMIDES, POLYSTRYENE, POLYVINYL CHLORIDE, AND POLYOLEFINS AND WHICH HAS A TENDENCE TO ACCUMULATE STATIC ELECTRICITY AND, INCORPORATED THEREIN, 0.01 TO 5% BY WEIGHT OF THE POLYMER OF AN ANTISTATIC COMPOUND OF THE FORMULA
 2. A composition according to claim 1 wherein the antistatic compound is present in an amount of 0.1 to 1% by weight of the polymer.
 3. A composition according to claim 1 wherein the antistatic compound is a compound of the formula C11H23CONH(CH2)3NH(CH2)3NHCH2COONa and the polymer is a polyamide.
 4. A composition according to claim 1 wherein the antistatic compound is a compound of the formula
 5. A composition according to claim 1 wherein the antistatic compound is a compound of the formula
 6. A composition according to claim 1 wherein the antistatic compound is a compound of the formula
 7. A composition according to claim 1 wherein the antistatic compound is a compound of the formula
 8. A composition according to claim 1 wherein the antistatic compound is a compound of the formula C17H33CONH(CH2)3-NH-(CH2)3NHCH2COONa and the polymer is polyvinyl chloride.
 9. A composition according to claim 1 wherein the antistatic compound is a compound of the formula C17H33CONH(CH2)3NH(CH2)3NHCH2CH2COONa and the polymer is polyvinyl chloride.
 10. A composition according to claim 1 wherein the antistatic compound is a compound of the formula 